Lignins are present in the form of lignocelluloses in the plant bodies by complexation with celluloses and have the second largest reserve after celluloses as the carbon resource existing on the globe. At present, lignins are mainly produced as the by-products in the pulp producing process. There are various lignins, for example, lignin acetate and sulfolignin, according to the variety of pulping processes. These lignins have the chemical structures of decomposition and/or polycondensation of natural lignins with introduction of sulfonic acid and other relevant components. Because of the irregularly and significantly modified structures, the lignins have extremely limited applications, for example, dispersant or binder of cement.
The lignins as the important carbon resource having the second largest reserve after celluloses are recyclable and recoverable. It is thus highly demanded to separate the lignins in readily usable forms from lignocellulose materials. One proposed method disclosed in Japanese Patent Laid-Open No. H02-233701 separates lignin from a lignocellulose material while keeping the structural regularity of the lignin. This method contacts a lignocellulose material solvated in advance with a phenol compound with a concentrated acid to release the lignin from the lignocellulose material while preventing the lignin structure in the lignocellulose material from being significantly modified by the concentrated acid. This method introduces the phenol compound into a specific site of a phenylpropane unit as the basic skeleton of the lignin to produce a 1,1-diphenylpropane unit, and gives a low-molecular phenol derivative of the lignin (hereafter referred to as the lignophenol derivative) by cleavage of β-aryl ether linkage.
Several methods have been examined for separation of the lignophenol derivative from the reaction system by taking advantage of the low solubility of the lignophenol derivative in water. One method adds water to the reaction system to recover the lignophenol derivative as precipitate. Another method neutralizes the reaction system with addition of an alkali and extracts the lignophenol derivative. The precipitation-based separation process preferably adopts natural sedimentation for recovery of a maximum possible amount of the lignophenol derivative, but this requires a high volume of water and a number of processing steps. Another disadvantage of this process is failed recovery of a water-dissolved fraction of the lignophenol derivative. The alkali neutralization-based separation process, on the other hand, requires a high volume of water and has problems of gelation control and remaining cations.
In a purification process with an organic solvent, the lignophenol derivative is precipitated for purification in a nonpolar solvent, such as diethyl ether or hexane. There may, however, be a dissolved fraction of the lignophenol derivative in the nonpolar solvent. The nonpolar solvent with a low boiling point is not suitable for high-volume processing and has difficulty in recovery and reuse of the dissolved fraction of the lignophenol derivative in the nonpolar solvent. Evaporation is generally adopted for recovery of the lignophenol derivative from the organic solvent. This causes the problems of energy cost, safety, and disposal.
Various chemical modifications allow for the lignophenol derivative. Similar problems arise in separation and recovery of reaction products after such chemical modifications or in recovery of the lignophenol derivative from various lignophenol derivative-containing composite materials.
It would thus be demanded to provide a technique of effectively separating and recovering a lignin derivative with a 1,1-diphenylpropane unit and/or a unit derived from the 1,1-diphenylpropane unit from a lignin derivative-containing mixing system. There would be a demand for readily separating, producing, purifying, and recovering the lignin derivative from the lignin derivative-containing mixing system. There would also be a demand for efficiently separating, producing, purifying, and recovering the lignin derivative from the lignin derivative-containing mixing system. There would also be a demand for separating, producing, purifying, and recovering the lignin derivative from the lignin derivative-containing mixing system while restricting diffusion of an organic solvent. There would further be a demand for separating, producing, purifying, and recovering the lignin derivative from the lignin derivative-containing mixing system suitable for scaling-up.
The inventors of the present invention have found selective retention of the lignin derivative on a metal oxide in a lignin derivative-containing mixing system and completed the present invention to satisfy at least one of the above requirements by utilizing the metal oxide as a separating material of the lignin derivative as described below.
An aspect in accordance with the present invention provides a method for separating a lignin derivative comprising the step of contacting the lignin derivative with a metal oxide in a liquid medium and separating the metal oxide carrying the lignin derivative, wherein the lignin derivative having a 1,1-diphenylpropane unit and/or the unit derived from the 1,1-diphenylpropane unit.
In the separation method of the invention, the metal oxide may be the oxide of one or more metals selected from the group consisting of titanium, zinc, iron, cobalt, nickel, copper, tin, indium, lead, and niobium. Preferably, the metal oxide comprises a titanium oxide. Further, the metal oxide may comprise a semiconductor material. The metal oxide may comprise a metal oxide particle of average particle size of not greater than 300 nm.
Further, in the separation method of the invention, the liquid medium can be selected from the group consisting of aqueous medium, non-aqueous medium and mixture thereof and the lignin derivative may be dissolved or dispersed in the liquid medium.
Still further, in the separation method of the invention, the lignin derivative can be one or more selected from the group consisting of following (a) to (d):    (a) a ligno-phenol derivative which is an phenol-derivative of lignin obtainable by solvating a lignin containing material with a phenol compound and then mixing the solvated lignin containing material with acid.    (b) a secondary derivative obtainable by introducing the ligno-phenol derivative a group selected from the group comprising acyl group, carboxy group, amido group, and cross-linking group.    (c) a secondary derivative obtainable by treating the ligno-phenol derivative with an alkali, and    (d) a higher order derivative obtainable by modifying the ligno-phenol derivative with at least two modifications selected from the following modifications:
introduction of acyl group, introduction of carboxy group, introduction of amido group, introduction of cross-linking group and alkali-treatment.
Preferably, the lignin derivative comprises the lignin derivative (a), the lignin derivative (b), or the lignin derivative (c).
Further, the separation method further comprises the step of separating and recovering the lignin derivative from the metal oxide.
Another aspect in accordance with the present invention provides a method for producing a lignin derivative comprising the step of contacting the lignin derivative with a metal oxide in a liquid medium and thereby separating the metal oxide carrying the lignin derivative, wherein the lignin derivative having a 1,1-diphenylpropane unit and/or the unit derived from the 1,1-diphenylpropane unit.
In the method of the invention, the lignin derivative can be the ligno-phenol derivative which is a phenol-derivative of lignin in a reaction medium obtainable by solvating a lignin containing material with a phenol compound and then mixing the solvated lignin containing material with acid. Further the separating step may comprise steps of producing the ligno-phenol derivative in a reaction medium obtainable by solvating a lignin containing material with a phenol compound and thereafter contacting the ligno-phenol derivative with the metal oxide and thereby separating the metal oxide carrying the lignin derivative.
Still another aspect in accordance with the present invention provides a method of purifying a lignin derivative comprising the step of contacting the lignin derivative with a metal oxide in a liquid medium and thereby separating the metal oxide carrying the lignin derivative, wherein the lignin derivative having a 1 ,1-diphenylpropane unit and/or the unit derived from the 1,1-diphenylpropane unit.
Another aspect in accordance with the present invention provides a method for producing a lignin derivative comprising the step of performing one or more modifications to the lignin derivative carried by the metal oxide, the modifications are selected from the following modifications, introduction of acyl group; introduction of carboxy group; introduction of amido group; introduction of cross-linking group; and alkali-treatment, wherein the lignin derivative having a 1,1-diphenylpropane unit and/or the unit derived from the 1,1-diphenylpropane unit. In the method of the invention, the modification can be performed to the lignin derivative carried on the metal oxide. Further, the modification steps keep the modified lignin derivative on the metal oxide.
Another aspect in accordance with the present invention provides a method for recovering a lignin derivative from a composite material containing thereof, comprising the step of contacting the lignin derivative with a metal oxide in a liquid medium and thereby separating the metal oxide carrying the lignin derivative, wherein the lignin derivative having a 1,1-diphenylpropane unit and/or the unit derived from the 1,1-diphenylpropane unit. In the method of the invention, the composite material may comprise a used product.
Still another aspect in accordance with the present invention provides a support for separation of a lignin derivative comprises a metal oxide.